Use of specific alcohol alkoxylates as an adjuvant for agrotechnical applications

ABSTRACT

The present invention relates to the use of specific amphiphilic alkoxyates as synergistic adjuvant for agrotechnical applications. Suitable agrotechnical compositions are also described. Thus, the addition of such alkoxylates makes possible an accelerated uptake of active ingredients by the plant. 
     The alkoxylates to be used are alkoxylates based on branched alcohols such as 2-propylheptanol, C 13 -oxo alcohols and C 10 -oxo alcohols.

The present invention relates to the use of specific amphiphilic alcoholalkoxylates as synergistic adjuvant for agrotechnical applications, inparticular in the field of crop protection. Suitable agrotechnicalcompositions are also described.

An important factor with a view to industrial production and applicationof active ingredients is, besides the optimization of the activeingredient's properties, the development of an efficacious composition.The expert formulation of the active ingredient(s) has the task ofcreating an ideal balance between properties such as bioactivity,toxicology, possible effects on the environment and costs, some of whichare contrary. Moreover, the shelf life and the user friendliness of acomposition is to a high degree determined by the formulation.

An aspect which is of particular importance for the activity of anagrotechnical composition is the effective uptake of the activeingredient by the plant. If uptake is via the leaf, a complex transportprocess results, in which the load of active ingredient, for exampleherbicide, must first penetrate the waxy cuticle of the leaf and mustsubsequently diffuse, via the cuticle, to the actual site of action inthe subjacent tissue.

The addition to formulations of certain auxiliaries in order to improvethe activity is generally known and agricultural practice. This has theadvantage that the amounts of active ingredient in the formulation canbe reduced while maintaining the activity of the latter, thus allowingcosts to be kept as low as possible and any official regulations to befollowed. In individual cases it is also possible to widen the spectrumof action since plants where the treatment with a particular activeingredient without addition was insufficiently successful can indeed betreated successfully by the addition of certain auxiliaries. Moreover,the performance may be increased in individual cases by a suitableformulation when the environmental conditions are not favorable. Thephenomenon that various active ingredients are not compatible with eachother in a formulation can therefore also be avoided.

Such auxiliaries are generally also referred to as adjuvants.Frequently, they take the form of surface-active or salt-like compounds.Depending on their mode of action, they can roughly be classified asmodifiers, actuators, fertilizers and pH buffers.

Modifiers affect the wetting, sticking and spreading properties of aformulation. Actuators break up the waxy cuticle of the plant andimprove the penetration of the active ingredient into the cuticle, bothshort-term (over minutes) and long-term (over hours). Fertilizers suchas ammonium sulfate, ammonium nitrate or urea improve the absorption andsolubility of the active ingredient and may reduce the antagonisticbehavior of active ingredients. pH buffers are conventionally used forbringing the formulation to an optimal pH.

Regarding the uptake of the active ingredient into the leaf,surface-active substances may act as modifiers and actuators. Ingeneral, it is assumed that suitable surface-active substances canincrease the effective contact area of liquids on leaves by reducing thesurface tension. Moreover, surface-active substances can dissolve orbreak up the epicuticular waxes, which facilitates the absorption of theactive ingredient. Furthermore, some surface-active substances can alsoimprove the solubility of active ingredients in formulations and thusavoid, or at least delay, crystallization. Finally, they can also affectthe absorption of active ingredients in some cases by retainingmoisture.

Surfactant-type adjuvants are exploited in a number of ways foragrotechnical applications. They can be divided into groups of anionic,cationic, nonionic or amphoteric substances.

Substances which are traditionally used as activating adjuvants arepetroleum-based oils. More recently, seed extracts, natural oils andtheir derivatives, for example of soybeans, sunflowers and coconut, havealso been employed.

Synthetic surface-active substances which are conventionally used asactuators take the form of, inter alia, polyoxyethylene condensates withalcohols, alkylphenols or alkylamines with HLB values in the range offrom 8 to 13. In this context WO 00/42847, for example, mentions the useof specific linear alcohol alkoxylates in order to increase the activityof agrotechnical biocide formulations. EP-A 0 356 812 describesadjuvants which are said to comprise not only an anionic surfactant, butalso a nonionic surfactant. Nonionic surfactants which are consideredsuitable are polyalkoxylated C₆-C₂₂-alkyl ethers.

However, the alcohol alkoxylates cover a wide spectrum. As surfactants,they are predominantly used in cleaners and detergents, in themetalworking industry, in the production and processing of textiles, inthe leather industry, in papermaking, in the printing industry, in theelectroplating industry and in the photographic industry, in thetreatment of water, in pharmaceutical formulations, formulations forveterinary use and crop protection formulations, or in thepolymer-producing and -processing industries. In particular thestructures of the alcohol moiety, and in some cases also of thealkoxylate moiety, affect the properties of the alkoxylates, so thatvarious technical effects can be exploited in the above-mentionedapplications. These include wetting, spreading, penetration, adhesion,film formation, the improvement of compatibilities, drift control anddefoaming.

Thus, for example, WO 01/77276, U.S. Pat. No. 6,057,284 and U.S. Pat.No. 5,661,121 describe certain alcohol alkoxylates as foam-reducingsurfactants. These surfactants are block alkoxylates whose alcoholmoiety is branched.

It is an object of the present invention to provide further uses of suchalkoxylates which are based on branched alcohols.

We have found that this object is achieved by using the alkoxylates asadjuvant and by providing agrotechnical compositions comprising thesealkoxylates.

The present invention therefore relates to the use of at least onealkoxylated branched alcohol as adjuvant in the treatment of plants.

The alkoxylates to be used in accordance with the invention haveadjuvant, in particular synergistic, properties. Thus, the addition ofsuch alkoxylates makes possible an accelerated uptake of activeingredients by a plant to be treated with the active ingredient. Theadjuvant action results in particular in the following aspects in thetreatment of plants with one or more active ingredients:

-   -   in comparison higher activity of the active ingredient for a        given application rate;    -   in comparison lower application rate with a given effect;    -   in comparison better uptake of the active ingredient by the        plant, in particular via the leaf, and thus advantages for the        post-emergence treatment, in particular the spray treatment of        plants.

The use according to the invention aims in particular at plantcultivation, agriculture and horticulture. It is intended in particularfor controlling undesired plant growth.

Accordingly, the present invention also relates to methods, for thetreatment of plants, which correspond to the above intended uses, asuitable amount of alkoxylate according to the invention being applied.

Particular advantages are achieved in particular in the production ofAllium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis,Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napusvar. napus, Brassica napus var. napobrassica, Brassica rapa var.silvestris, Camellia sinensis, Carthamus tinctorius, Caryaillinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffeacanephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucuscarota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypiumhirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypiumvitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare,Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linumusitatissimum, Lycopersicon lycopersicum, Malus spec., Manihotesculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica),Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris,Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica,Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharumofficinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s.vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum,Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

In addition, the alkoxylates to be used in accordance with the inventionmay also be used in crops which tolerate the effect of herbicides. Suchcrops can be obtained for example by breeding and also by recombinantmethods.

At least some of the alkoxylates to be used are known per se. Forexample WO 01/77276 and U.S. Pat. No. 6,057,284 or EP 0 906 150 describesuitable alkoxylates. The description of these alkoxylates in thesepublications is herewith expressly referred to, whereby the alkoxylatesthemselves which are disclosed therein and also their preparation areincorporated into the present disclosure.

As a rule, the alcohol moiety of the alcohol alkoxylates to be used inaccordance with the invention is based on alcohols or alcohol mixturesknown per se which have 5 to 30, preferably 8 to 20, in particular 10 to13, carbon atoms. Fatty alcohols having approximately 8 to 20 carbonatoms must be mentioned in particular. As is known, many of these fattyalcohols are employed in the production of nonionic and anionicsurfactants, to which end the alcohols are subjected to suitablefunctionalization, for example by alkoxylation or glycosidation.

The alcohol moiety of the alkoxylates to be used is branched. Thus, themain chain of the alcohol moiety has, as a rule, 1 to 4 branchings, italso being possible to use alcohols with a higher or lower degree ofbranching in a mixture with other alcohol alkoxylates as long as themean number of branchings of the mixture is in the above-stated range.

In general, the branchings independently of one another have 1 to 10,preferably 1 to 6, in particular 1 to 4, carbon atoms. Particularbranchings are methyl, ethyl, n-propyl or isopropyl groups.

In accordance with one embodiment, the alcohol moieites on which thealkoxylates are based thus have an average of at least two terminalmethyl groups.

Suitable alcohols and, in particular, fatty alcohols are obtainable bothfrom natural sources, for example by obtaining and, if required ordesired, by hydrolyzing, transesterifying and/or hydrogenatingglycerides and fatty acids, and by synthetic routes, for example bybuilding up from starting materials having a smaller number of carbonatoms. Thus, for example, the SHOP process (Shell Higher Olefin Process)gives, starting from ethene, olefin fractions having a number of carbonatoms suitable for further processing to produce surfactants. Thefunctionalization of the olefins to form the corresponding alcohols iscarried out, for example, by hydroformylation and hydrogenation.

Olefins having a number of carbon atoms suitable for further processingto give suitable alcohols can also be obtained by oligomerization ofC₃-C₆-alkenes, in particular propene or butene or mixtures of these.

Moreover, lower olefins can be oligomerized by means of heterogeneous,acidic catalysts, e.g. supported phosphoric acid, and subsequentlyfunctionalized to give alcohols.

A general possibility of synthesizing to produce branched alcohols is,for example, the reaction of aldehydes or ketones with Grignard reagents(Grignard synthesis). Instead of Grignard reagents, it is also possibleto employ aryllithium or alkyllithium compounds, which are distinguishedby higher reactivity. Moreover, the branched alcohols can be obtained byaldol condensation, the skilled worker being familiar with the reactionconditions.

The alkoxylation is the result of the reaction with suitable alkyleneoxides which, as a rule, have 2 to 15, preferably 2 to 6, carbon atoms.The following may be mentioned in particular in this context: ethyleneoxide (EO), propylene oxide (PO), butylene oxide (BO), pentylene oxide(PeO) and hexylene oxide (HO).

One type of alcohol alkoxylate to be used is based on one type ofalkylene oxide.

A further type of alcohol alkoxylate to be used is based on at least twodifferent types of alkylene oxide. It is preferred in this context toarrange several alkylene oxide units of one type as a block, resultingin at least two different alkylene oxide blocks, each of which is formedby several units of identical alkylene oxides. If such block alkoxylatesare used, it is preferred that the alkylene oxide moiety is composed of3, in particular 2, blocks.

According to one aspect, it is preferred that the alcohol alkoxylates tobe used in accordance with the invention are ethoxylated or have atleast one ethylene oxide block. According to a further aspect, ethyleneoxide blocks are combined in particular with propylene oxide blocks orpentylene oxide blocks.

The respective degree of alkoxylation is a function of the amounts ofalkylene oxide(s) chosen for the reaction and the reaction conditions.It is, as a rule, a statistic mean since the number of alkylene oxideunits of the alcohol alkoxylates resulting from the reaction varies.

The degree of alkoxylation, i.e. the mean chain length of the polyetherchains of alcohol alkoxylates to be used in accordance with theinvention, can be determined by the molar ratio of alcohol to alkyleneoxide. Preferred alcohol alkoxylates are those having approximately 1 to100, preferably approximately 2 to 15, in particular 3 to 12, mainly 4to 12 and especially 5 to 12 alkylene oxide units.

The alcohols, or alcohol mixtures, are reacted with the alkyleneoxide(s) by customary methods with which the skilled worker is familiarand in apparatuses conventionally used for this purpose.

The alkoxylation may be catalyzed by strong bases such as alkali metalhydroxides and alkaline earth metal hydroxides, Brönsted acids or Lewisacids, such as AlCl₃, BF₃ and the like. Catalysts such as hydrotalciteor DMC may be used for alcohol oxylates with a narrow distribution.

The alkoxylation is preferably carried out at temperatures in the rangeof from approximately 80 to 250° C., preferably approximately 100 to220° C. The pressure range is preferably between atmospheric pressureand 600 bar. If desired, the alkylene oxide may comprise an admixture ofinert gas, for example of from approximately 5 to 60%.

Accordingly, the alkoxylated branched alcohols to be used are selectedin particular among alcohol alkoxylates of the formula (I)

R—O—(C_(m)H_(2m)O)_(x)—(C_(n)H_(2n)O)_(y)—(C_(p)H_(2p)O)_(z)—H  (I)

in which

-   R is branched C₅-C₃₀-alkyl;-   m, n, p independently of one another are an integer from 2 to 16,    preferably 2, 3, 4 or 5;-   x+y+z have a value of 1 to 100,    and the embodiments of alcohol alkoxylates of the formula (I) which    result taking into consideration what has been said above.

In accordance with a particular embodiment, alcohol alkoxylates of theformula (I) are used in which m=2 and the value of x is greater thanzero. These are alcohol alkoxylates of the EO type, which include mainlyalcohol ethoxylates (m=2; x>zero; y, z=zero) and alcohol alkoxylateswith an EO block bonded to the alcohol moiety (m=2; x>zero; y and/orz>zero). Substances which must be mentioned among the alcoholalkoxylates with an EO block bonded to the alcohol moiety are mainlyEO/PO block alkoxylates (m=2; x>zero; y>zero; n=3; z=0), EO/PeO blockalkoxylates (m=2; x>zero; y>zero; n=5; z=0) and EO/PO/EO blockalkoxylates (m, p=2; x, z>zero; y>zero; n=3).

Preferred substances are EO/PO block alkoxylates in which the EO:POratio (x:y) is 1:1 to 4:1, in particular 1.5:1 to 3:1. In this context,the degree of ethoxylation (value of x) is, as a rule, 1 to 20,preferably 2 to 15, in particular 4 to 10, and the degree ofpropoxylation (value of y) is, as a rule, 1 to 20, preferably 1 to 8, inparticular 2 to 5. The total degree of alkoxylation, i.e. the total ofEO and PO units, is, as a rule, 2 to 40, preferably 3 to 25, inparticular 6 to 15.

Furthermore preferred are EO/PeO block alkoxylates in which the EO:PeOratio (x:y) is 2:1 to 25:1, in particular 4:1 to 15:1. In this context,the degree of ethoxylation (value of x) is, as a rule, 1 to 50,preferably 4 to 25, in particular 6 to 15, and the degree ofpentoxylation (value of y) is, as a rule, 0.5 to 20, preferably 0.5 to4, in particular 0.5 to 2. The total degree of alkoxylation, i.e. thetotal of EO and PeO units, is, as a rule, 1.5 to 70, preferably 4.5 to29, in particular 6.5 to 17.

In accordance with a further particular embodiment, alcohol alkoxylatesof the formula (I) are used in which n=2, the values of x and y are bothgreater than zero and z=0. Again, these alcohol alkoxylates take theform of the EO type, with the EO block being bonded terminally, however.These include mainly PO/EO block alkoxylates (n=2; x>zero; y>zero; m=3;z=0) and PeO/EO block alkoxylates (n=2; x>zero; y>zero; m=5; z=0).

Preferred PO/EO block alkoxylates are those in which the PO:EO ratio(x:y) is 1:10 to 3:1, in particular 1.5:1 to 1:6. In this context, thedegree of ethoxylation (value of y) is, as a rule, 1 to 20, preferably 2to 15, in particular 4 to 10, and the degree of propoxylation (value ofx) is, as a rule, 0.5 to 10, preferably 0.5 to 6, in particular 1 to 4.The total degree of alkoxylation, i.e. the total of EO and PO units, is,as a rule, 1.5 to 30, preferably 2.5 to 21, in particular 5 to 14.

Furthermore preferred are PeO/EO block alkoxylates in which the PeO:EOratio (x:y) is 1:50 to 1:3, in particular 1:25 to 1:5. In this context,the degree of pentoxylation (value of x) is, as a rule, 0.5 to 20,preferably 0.5 to 4, in particular 0.5 to 2, and the degree ofethoxylation (value of y) is, as a rule, 3 to 50, preferably 4 to 25, inparticular 5 to 15. The total degree of alkoxylation, i.e. the total ofEO and PeO units, is, as a rule, 3.5 to 70, preferably 4.5 to 45, inparticular 5.5 to 17.

In accordance with a further particular embodiment, alcohol alkoxylatesof the formula (I) are used in which the values of x, y and z are allgreater than zero. These include mainly PeO/EO/PO block alkoxylates(m=5; x>zero; n=2; y>zero; m=3; z>zero).

In accordance with a preferred embodiment, the alcohol alkoxylates to beused in accordance with the invention are based on primary, α-branchedalcohols of the formula (II)

in which

-   R¹, R² independently of one another are hydrogen or C₁-C₂₆-alkyl.

Preferably, R¹ and R² independently of one another are C₁-C₆-alkyl, inparticular C₂-C₄-alkyl.

Very especially preferred are alcohol alkoxylates which are based on2-propylheptanol. These include, in particular, alcohol alkoxylates ofthe formula (I) in which R is a 2-propylheptyl radical, i.e. R¹ and R²in formula (II) are in each case n-propyl.

Such alcohols are also referred to as Guerbet alcohols. They can beobtained for example by dimerization of corresponding primary alcohols(for example R^(1,2) CH₂CH₂OH) at elevated temperature, for example 180to 300° C., in the presence of an alkaline condensing agent such aspotassium hydroxide.

Alkoxylates which are employed for the purposes of this preferredembodiment, which is based on Guebert alcohols, are mainly alkoxylatesof the EO type. Particularly preferred are ethoxylates with a degree ofethoxylation of 1 to 50, preferably 2 to 20, in particular approximately3 to 10. The correspondingly ethoxylated 2-propylheptanols may bementioned especially among these.

In accordance with a further preferred embodiment, the alcoholalkoxylates to be used are based on C₁₃-oxo alcohols.

As a rule, the term “C₁₃-oxo alcohol” refers to an alcohol mixture whosemain component is formed by at least one branched C₁₃-alcohol(isotridecanol). Such C₁₃-alcohols include, in particular,tetramethylnonanols, for example 2,4,6,8-tetramethyl-1-nonanol or3,4,6,8-tetramethyl-1-nonanol and furthermore ethyldimethylnonanols suchas 5-ethyl-4,7-dimethyl-1-nonanol.

Suitable C₁₃-alcohol mixtures can generally be obtained by hydrogenationof hydroformylated trimeric butene. In particular, it is possible toproceed as follows:

-   a) butenes are brought into contact with a suitable catalyst for    oligomerization,-   b) a C₁₂-olefin fraction is isolated from the reaction mixture,-   c) the C₁₂-olefin fraction is hydroformylated by reaction with    carbon monoxide and hydrogen in the presence of a suitable catalyst,    and-   d) hydrogenated.

Advantageous C₁₃-alcohol mixtures are essentially free from halogens,i.e. they contain less than 3 ppm by weight, in particular less than 1ppm by weight, of halogen, in particular chlorine.

The butene trimerization can be carried out with homogeneous orheterogeneous catalysis.

In the DIMERSOL process (cf. Revue de l'Institut Francais du Petrole,Vol. 37, No. 5, September/October 1982, pp. 639ff), butenes areoligomerized in a homogeneous phase in the presence of a catalyst systemcomprising a transition metal derivative and an organometallic compound.Typical catalyst systems are Ni(O) complexes in combination with Lewisacids such as AlCl₃, BF₃, SbF₅ and the like, or Ni(II) complexes incombination with alkylaluminum halides.

However, it is also possible to oligomerize butenes in the manner knownper se using a heterogeneous nickel-containing catalyst (process stepa). Depending on the selected reaction conditions, different relativeamounts of butene dimers, trimers and higher oligomers are obtained. Thebutene trimers, i.e. C₁₂-olefins, are further processed for the presentpurposes. The isobutene content may be selected with a view to thedesired degree of branching of the C₁₃-alcohol mixture obtained afterthe hydroformylation/−hydrogenation. Relatively low degrees of branchingrequire a relatively low isobutene content and vice versa. If, forexample, the C₁₂-olefin fraction is to have an ISO index ofapproximately 1.9 to 2.3, it is expedient to select predominantly linearbutenes, i.e. the hydrocarbon stream which is generally employed shouldcontain less than 5% by weight of isobutene based on the butenefraction. The butenes may contain an admixture of saturatedC₄-hydrocarbons, which act as diluent in the oligomerization process.

The heterogeneous nickel-containing catalysts which may be used can havedifferent structures, with catalysts containing nickel oxide beingpreferred. Catalysts which are known per se as described in C. T.O'Connor et al., Catalysis Today, vol. 6 (1990), pp. 336-338 aresuitable.

The hydrocarbon stream (preferably C₄) comprises, as a rule, from 50 to100% by weight, preferably from 60 to 90% by weight, of butenes and from0 to 50% by weight, preferably from 10 to 40% by weight, of butanes. Thebutene fraction contains less than 5% by weight, in particular less than3% by weight, of isobutene, based on the butene fraction. The butenefraction generally has the following composition (in each case based onthe butene fraction):

1-butene 1 to 50% by weight cis-2-butene 1 to 50% by weighttrans-2-butene 1 to 99% by weight isobutene  1 to 5% by weight

A particularly preferred starting material which is employed is what isknown as raffinate II, which is an isobutene-depleted C₄ fraction froman FCC plant or a steam cracker.

Starting with the material obtained in the oligomerization reaction, aC₁₂-olefin fraction is isolated in one or more separation steps (processstep b). Suitable separation devices are the usual apparatuses familiarto the skilled worker. These include, for example, distillation columnssuch as tray columns which may, if desired, be equipped with bubblecaps, sieve plates, sieve trays, valves, side offtakes and the like,evaporators such as thin-film evaporators, falling-film evaporators,wiper-blade evaporators, Sambay evaporators and the like, andcombinations thereof. The C₁₂-olefin fraction is preferably isolated byfractional distillation.

The ISO index of the C₁₂-olefin fraction, which indicates the meannumber of branchings, is generally from 1 to 4, preferably 1.9 to 2.3,in particular 2.0 to 2.3. The ISO index can be determined, for example,by hydrogenating a sample of the C₁₂-olefin fraction to give thedodecanes and determining the mean number of methyl groups with the aidof the signal area attributable to the methyl groups and the signal areaattributable to the total of the protons in the ¹H-NMR spectrum. The ISOindex is the mean number of methyl groups minus two.

To prepare an alcohol mixture according to the invention, the C₁₂-olefinfraction which has been isolated is hydroformylated to giveC₁₃-aldehydes (process step c), and these are subsequently hydrogenatedto form C₁₃-alcohols (process step d). The preparation of the alcoholmixture can be carried out in a single step or in two separate reactionsteps.

An overview of hydroformylation processes and suitable catalysts can befound in Beller et al., Journal of Molecular Catalysis A 104 (1995), pp.17-85.

The hydroformylation is preferably carried out in the presence of acobalt hydroformylation catalyst. The amount of the hydroformylationcatalyst is generally from 0.001 to 0.5% by weight, calculated as cobaltmetal and based on the amount of the olefins to be hydroformylated. Thereaction temperature is generally in the range of from about 100 to 250°C., preferably from 150 to 210° C. The reaction may be carried out at asuperatmospheric pressure of from about 10 to 650 bar. Thehydroformylation is preferably carried out in the presence of water;however, it may also be carried out in the absence of water.

Carbon monoxide and hydrogen are usually used in the form of a mixtureknown as synthesis gas. The composition of the synthesis gas employedcan vary within a wide range. The molar ratio of carbon monoxide tohydrogen is generally from approximately 2.5:1 to 1:2.5. A preferredratio is about 1:1.5.

The cobalt catalyst which is dissolved homogeneously in the reactionmedium can be separated from the hydroformylation product in a suitablemanner by treating the reaction product of the hydroformylation processwith oxygen or air in the presence of an acidic aqueous solution. Thisdestroys the cobalt catalyst by oxidation to give cobalt(II) salts. Thecobalt(II) salts are water-soluble and are extracted into the aqueousphase, which can be separated off and returned to the hydroformylationprocess.

The crude aldehydes or aldehyde/alcohol mixtures obtained in thehydroformylation can, if desired, be isolated before hydrogenation bycustomary methods known to the skilled worker and, if appropriate,purified.

For the hydrogenation, the reaction mixtures obtained in thehydroformylation are reacted with hydrogen in the presence ofhydrogenation catalysts.

Suitable hydrogenation catalysts are generally transition metals suchas, for example, Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru and the like ormixtures of these, which may be applied to supports such as activecharcoal, aluminum oxide, kieselguhr and the like, to increase activityand stability. To increase the catalytic activity, it is possible to useFe, Co and, preferably, Ni as metal sponge having a very high surfacearea, including these metals in the form of the Raney catalysts. A Co/Mocatalyst is preferably employed for the preparation of the surfactantalcohols according to the invention. Depending on the activity of thecatalyst, the oxo aldehydes are preferably hydrogenated at elevatedtemperatures and superatmospheric pressures. The hydrogenationtemperature is preferably at about 80 to 250° C., and the pressure ispreferably at approximately 50 to 350 bar.

Further suitable C₁₃-alcohol mixtures can be obtained by proceeding asfollows:

-   a) subjecting a C₄-olefin mixture to metathesis,-   b) separating olefins having 6 C atoms from the metathesis mixture,-   c) subjecting the olefins which have been separated off,    individually or as a mixture, to a dimerization to give olefins    mixtures having 12 C atoms, and-   d) subjecting the resulting olefin mixture, if appropriate after    fractionation, to derivatization to give a C₁₃-oxo alcohol mixture.

The principles of the metathesis employed in process step a) have beendescribed for example in Ullmann's Encyclopedia of Industrial Chemistry,5th Ed., Vol. A18, pp. 235/236. More information on how this process iscarried out can be found in, for example, K. J. Ivin, “OlefinMetathesis, Academic Press, London, (1983); Houben-Weyl, E18, 1163-1223;R. L. Banks, Discovery and Development of Olefin Disproportionation,CHEMTECH (1986), February, 112-117.

When applying metathesis to the main constituents but-1-ene andbut-2-ene present in the C₄-olefin streams, olefins having 5 to 10 Catoms, preferably 5 to 8 C atoms, but in particular pent-2-ene andhex-3-ene, are formed in the presence of suitable catalysts.

Suitable catalysts are preferably molybdenum, tungsten or rheniumcompounds. It is particularly expedient to carry out the reaction withheterogeneous catalysis, the catalytically active metals being employedin particular with Al₂O₃ or SiO₂ supports. Examples of such catalystsare MoO₃ or WO₃ on SiO₂, or Re₂O₇ on Al₂O₃.

It is particularly advantageous to carry out the metathesis in thepresence of a rhenium catalyst, since this allows particularly mildreaction conditions to be used. Thus, the metathesis may be carried outin this case at a temperature of from 0 to 50° C. and at low pressuresof from approx. 0.1 to 0.2 MPa.

The dimerization of the olefins or olefin mixtures obtained in themetathesis step gives dimerization products which have particularlyfavorable components and a particularly advantageous compositions with aview to further processing into surfactant alcohols when a dimerizationcatalyst is employed which contains at least one element from groupVIIIb of the Periodic Table and when the catalyst composition and thereaction conditions are chosen in such a way that a dimer mixture isobtained with less than 10% by weight of compounds which contain astructural element of the formula III (vinylidene group)

where A¹ and A² are aliphatic hydrocarbon radicals.

The internal linear pentenes and hexenes present in the metathesisproduct are preferably employed for the dimerization reaction. The useof hex-3-ene is particularly preferred.

The dimerization reaction can be carried out with homogeneous orheterogeneous catalysis. The heterogeneous procedure is preferred fortwo reasons, firstly because separation of the catalyst is simplified,thus making the procedure more economical, and secondly because nopolluting wastewaters as are usually obtained when separating offdissolved catalysts, for example by hydrolysis, are generated. A furtheradvantage of the heterogeneous procedure is the fact that thedimerization product contains no halogens, in particular chlorine orfluorine. Homogeneously soluble catalysts generally containhalide-containing ligands or are employed in combination withhalogen-containing cocatalysts. Halogen from such catalyst systems maybe incorporated into the dimerization products, which has a considerableadverse effect not only on product quality, but also on furtherprocessing steps, in particular the hydroformylation to give surfactantalcohols.

The heterogeneous catalysis expediently involves the use of combinationsof oxides of metals of group VIIIb with aluminum oxide on supportmaterials made of silicon oxides and titanium oxides as are known, forexample, from DE-A-43 39 713. The heterogeneous catalyst may be employedin a solid bed, in which case it is preferably coarsely particulate aspellets of 1 to 1.5 mm, or in suspension (particle size 0.05 to 0.5 mm).When following the heterogeneous route, the dimerization is preferablycarried out in a closed system at temperatures of from 80 to 200° C.,preferably from 100 to 180° C., under the pressure which prevails at thereaction temperature or, if appropriate, under protective gas atsuperatmospheric pressure. To obtain optimum conversion rates, thereaction mixture is circulated repeatedly, a particular proportion ofthe circulating product continuously being drawn off and replaced bystarting material.

The dimerization gives mixtures of monounsaturated hydrocarbons, withthe chain lengths of the components being predominantly twice that ofthe starting olefins.

The dimerization catalysts and reaction conditions are expedientlychosen in such a way within the context of what has been said that atleast 80% of the components of the dimerization mixture have onebranching, or two branchings at adjacent C atoms, over ¼ to ¾,preferably ⅓ to ⅔, of the chain length of their main chain.

The high percentage—as a rule more than 75%, in particular more than80%—of components with branchings and the low percentage—as a rule lessthan 25%, in particular less than 20%—of unbranched olefins is highlycharacteristic of the olefin mixtures thus produced. A furthercharacteristic is that predominantly groups with (y-4) and (y-5) C atomsare bonded to the branching sites of the main chain, y being the numberof carbon atoms of the monomer employed in the dimerization process. Thevalue (y-5)=0 means that no side chain is present.

The main chain of the C₁₂-olefin mixtures thus prepared preferably hasmethyl or ethyl groups at the branching points.

The position of the methyl and ethyl groups on the main chain is alsocharacteristic. In the case of monosubstitution, the methyl or ethylgroups are in position P=(n/2)−m of the main chain, n being the lengthof the main chain and m the number of carbon atoms of the side groups,while in the case of disubstitution products one substituent is locatedat position P and the other at the adjacent carbon atom P+1. Thepercentages of monosubstitution products (single branching) in theolefin mixture prepared in accordance with the invention arecharacteristically all in the range of from 40-75% by weight, and thepercentages of doubly branched components is in the range of from 5 to25% by weight.

It has furthermore been found that the dimerization mixtures areparticularly accessible to further derivatization when the position ofthe double bond meets certain requirements. In these advantageous olefinmixtures, the position of the double bonds relative to the branchings ischaracterized in that the ratio of the “aliphatic” hydrogen atoms to“olefinic” hydrogen atoms is in the rangeH_(aliph.):H_(olefin.)=(2*n−0.5):0.5 to (2*n−1.9):1.9, n being thenumber of carbon atoms of the olefin resulting from the dimerizationprocess.

(Hydrogen atoms referred to as “aliphatic” are hydrogen atoms which arebonded to carbon atoms which do not form part of a C═C-double bond (Pibond), while “olefinic” hydrogen atoms are those which are bonded to acarbon atom which actuates a Pi bond).

Especially preferred dimerization mixtures are those in which the ratio

H_(aliph.):H_(olefin.)=(2*n−1.0):1 to (2*n−1.6):1.6.

The olefin mixtures thus produced are first hydroformylated by reactionwith carbon monoxide and hydrogen in the presence of suitable catalysts,preferably cobalt- or rhodium-containing catalysts, to give surfactantalcohols (oxo alcohols), branched primary alcohols.

A good overview of the method of hydroformylation, including a number offurther references, can be found for example in the comprehensive essayby Beller et al. in Journal of Molecular Catalysis, A104 (1995) 17-85 orin Ullmanns Encyclopedia of Industrial Chemistry, Vol. A5 (1986), page217 ff., page 333, and the literature referred to.

Owing to the comprehensive information provided therein, it is possiblefor the skilled worker also to hydroformylate the branched olefinsaccording to the invention. In this reaction, CO and hydrogen undergo anaddition reaction with olefinic double bonds, giving rise to mixtures ofaldehydes and alkanols as shown in the reaction scheme below:

The molar ratio of n- and iso-compounds in the reaction mixture isusually in the range of from 1:1 to 20:1, depending on the selectedprocess conditions for the hydroformylation and the catalyst employed.The hydroformylation is usually carried out in the temperature range offrom 90 to 200° C. and at a CO/H₂ pressure of from 2.5 to 35 MPa (25 to350 bar). The mixing ratio of carbon monoxide to hydrogen depends onwhether the reaction is intended to yield predominantly alkanals oralkanols. The process is expediently carried out in a CO:H range of from10:1 to 1:10, preferably 3:1 to 1:3, the range of the lower partialpressures of hydrogen being selected if alkanals are to be prepared andthe range of the higher partial pressures of hydrogen, for exampleCO:H₂=1:2, being chosen if alkanols are to be prepared.

Suitable catalysts are, mainly, metal compounds of the general formulaHM(CO)₄ or M₂(CO)₈ where M is a metal atom, preferably a cobalt, rhodiumor ruthenium atom.

In general, the catalysts or catalyst precursors employed in each casegive, under hydroformylation conditions, catalytically active species ofthe general formula H_(x)M_(y)(CO)_(z)L_(q) in which M is a metal ofgroup VIIIb, L is a ligand which may be a phosphine, phosphite, amine,pyridine or any other donor compound, also in polymeric form, and q, x,y and z are integers which depend on the valency and type of the metaland on the binding ability of the ligand L, it also being possible for qto be 0.

The metal M is preferably cobalt, ruthenium, rhodium, palladium,platinum, osmium or iridium, in particular cobalt, rhodium or ruthenium.

Examples of suitable rhodium compounds or complexes are rhodium(II) andrhodium(III) salts such as rhodium(III) chloride, rhodium(III) nitrate,rhodium(III) sulfate, potassium rhodium sulfate, rhodium(II)carboxylate, rhodium(III) carboxylate, rhodium(II) acetate, rhodium(III)acetate, rhodium(III) oxide, salts of rhodic(III) acid, such as, forexample, trisammonium hexachlororhodate(III). Others which are suitableare rhodium complexes such as rhodiumbiscarbonyl acetylacetonate,acetylacetonatobisethylenerhodium(I). Rhodiumbiscarbonylacetylacetonateor rhodium acetate are preferably employed.

Examples of suitable cobalt compounds are cobalt(II) chloride,cobalt(II) sulfate, cobalt(II) carbonate, cobalt(II) nitrate, theiramine or hydrate complexes, cobalt carbocyclates such as cobalt acetate,cobalt ethylhexanoate, cobalt naphthanoate and the cobalt caprolactamatecomplex. The carbonyl complexes of cobalt, such as dicobaltoctocarbonyl,tetracobaltdodecacarbonyl and hexacobalthexadecacarbonyl, may also beemployed for this purpose.

The abovementioned cobalt, rhodium and ruthenium compounds are known inprinciple and are described sufficiently in the literature or else canbe prepared by the skilled worker in analogy to the known compounds.

The hydroformylation can be carried out with addition of inert solventsor diluents or without such an addition. Examples of suitable inertadditions are acetone, methyl ethyl ketone, cyclohexanone, toluene,xylene, chlorobenzene, methylene chloride, hexane, petroleum ether,acetonitrile and the high-boiling fractions obtained in thehydroformylation of the dimerization products.

If the aldehyde content of the resulting hydroformylation product isunduly high, this may be remedied simply by hydrogenation, for exampleusing hydrogen in the presence of Raney nickel or using other catalystswhich are known for hydrogenation reactions, in particular catalystscontaining copper, zinc, cobalt, nickel, molybdenum, zirconium ortitanium. Most of the aldehyde fraction present is hydrogenated to givealkanols. If the aldehyde fraction in the reaction mixture is to bevirtually eliminated, this can be achieved, if desired, by a secondhydrogenation process, for example using an alkali metal borohydrideunder particularly mild and economical conditions.

The pure C₁₃-alcohol mixture according to the invention can be obtainedfrom the reaction mixture which results from the hydrogenation processby customary purification methods known to the skilled worker, inparticular by fractional distillation.

As a rule, C₁₃-alcohol mixtures according to the invention have a meandegree of branching of from 1 to 4, preferably from 2.1 to 2.5, inparticular from 2.2 to 2.4. The degree of branching is defined as thenumber of methyl groups in one molecule of the alcohol minus 1. The meandegree of branching is the statistical mean of the degrees of branchingof the molecules of a sample. The mean number of methyl groups in themolecules of a sample can be determined readily by ¹H-NMR spectroscopy.For this purpose, the signal area corresponding to the methyl protons inthe ¹H-NMR spectrum of a sample is divided by three and then divided bythe signal area of the methylene protons if the CH₂—OH group divided bytwo.

Preferred within this embodiment, which is based on C₁₃-oxo alcohols,are in particular those alcohol alkoxylates which are either ethoxylatedor which are block alkoxylates of the EO/PO type.

The degree of ethoxylation of the ethoxylated C₁₃-oxo alcohols to beused in accordance with the invention is, as a rule, 1 to 50, preferably3 to 20 and in particular 3 to 10, mainly 4 to 10 and especially 5 to10.

The degrees of alkoxylation of the EO/PO block alkoxylates to be used inaccordance with the invention depends on the location of the blocks. Ifthe PO blocks are located terminally, the ratio between EO units and POunits is, as a rule, at least 1, preferably 1:1 to 4:1 and in particular1.5:1 to 3:1. The degree of ethoxylation here is, as a rule, 1 to 20,preferably 2 to 15 and in particular 4 to 10, and the degree ofpropoxylation is, as a rule, 1 to 20, preferably 1 to 8 and inparticular 2 to 5. The total degree of alkoxylation, i.e. the total ofEO and PO units, is, as a rule, 2 to 40, preferably 3 to 25 and inparticular 6 to 15. If, in contrast, the EO blocks are locatedterminally, the ratio between PO blocks and EO blocks is less criticaland is, as a rule, 1:10 to 3:1, preferably 1:1.5 to 1:6. In this case,the degree of ethoxylation is, as a rule, 1 to 20, preferably 2 to 15,in particular 4 to 10, and the degree of propoxylation is, as a rule,0.5 to 10, preferably 0.5 to 6, in particular 1 to 4. As a rule, thetotal degree of alkoxylation is 1.5 to 30, preferably 2.5 to 21 and inparticular 5 to 14.

In accordance with a further preferred embodiment, alcohol alkoxylateswhich are based on C₁₀-oxo alcohols are used.

Analogously to the term “C₁₃-oxo alcohol”, which has already beenexplained, the term “C₁₀-oxo alcohols” represents C₁₀-alcohol mixtureswhose main component is formed by at least one branched C₁₀-alcohol(isodecanol).

Suitable C₁₀-alcohol mixtures can generally be obtained by hydrogenationof hydroformylated trimeric propene. In particular, it is possible toproceed as follows:

-   a) propenes are brought into contact with a suitable catalyst for    oligomerization,-   b) a C₉-olefin fraction is isolated from the reaction mixture,-   c) the C₉-olefin fraction is hydroformylated by reaction with carbon    monoxide and hydrogen in the presence of a suitable catalyst, and-   d) hydrogenated.

Particular embodiments of this procedure result in analogy to theembodiments described above for the hydrogenation of hydroformylatedtrimeric butene.

It follows from what has been said above that in particular the C₁₃-oxoalcohols or the C₁₀-oxo alcohols to be used in accordance with theinvention are based on olefins which preexist in branched form. In otherwords, branchings cannot be attributed to the hydroformylation reactionalone, as would be the case in the hydroformylation of straight-chainolefins. This is why the degree of branching of alkoxylates to be usedin accordance with the invention is, as a rule, greater than 1.

As a rule, the alkoxylates to be used in accordance with the inventionhave a relatively small contact angle. Especially preferred alkoxylatesare those with a contact angle of less than 120°, preferably less than100°, when determined in the manner known per se using an aqueoussolution comprising 2% by weight of alkoxylate on a paraffin surface.

According to one aspect, the surface-active properties of thealkoxylates depend on the nature and distribution of the alkoxylategroup. The surface tension, as can be determined by the “pendant drop”method, of alkoxylates to be used in accordance with the invention ispreferably in a range of from 25 to 70 mN/m, in particular 28 to 50mN/m, for a solution comprising 0.1% by weight of alkoxylate, and in arange of from 25 to 70 mN/m, in particular 28 to 45 mN/m, for a solutioncomprising 0.5% by weight of alkoxylate. Alkoxylates to be used inaccordance with the invention thus qualify as amphiphilic substances.

Accordingly, the present invention also relates to compositionscomprising

-   (a) at least one active ingredient for the treatment of plants; and-   (b) at least one alkoxylated branched alcohol.

It is advantageous when component (b) amounts to more than 1% by weight,preferably more than 5% by weight and in particular more than 10% byweight based on the total weight of the composition. On the other hand,it is expedient, as a rule, when component (b) amounts to less than 50%by weight, preferably less than 45% by weight and in particular lessthan 40% by weight based on the total weight of the composition.

The active ingredient (component (a)) can be selected among herbicides,fungicides, insecticides, acaricides, nematicides, and activeingredients which regulate plant growth.

Herbicidal crop protection compositions may comprise, for example, oneor more of the following herbicidal crop protectants:

1,3,4-thiadiazoles such as buthidazole and cyprazole, amides such asallidochlor, benzoylpropethyl, bromobutide, chlorthiamid, dimepiperate,dimethenamid, diphenamid, etobenzanid, flamprop-methyl, fosamin,isoxaben, monalide, naptalame, pronamid, propanil, aminophosphoric acidssuch as bilanafos, buminafos, glufosinate-ammonium, glyphosate,sulfosate, aminotriazoles such as amitrol, anilides such as anilofos,mefenacet, aryloxyalkanoic acid such as 2,4-D, 2,4-DB, clomeprop,dichlorprop, dichlorprop-P, dichlorprop-P, fenoprop, fluoroxypyr, MCPA,MCPB, mecoprop, mecoprop-P, napropamide, napropanilide, triclopyr,benzoic acids such as chloramben, dicamba, benzothiadiazinones such asbentazone, bleachers such as clomazone, diflufenican, fluorochloridone,flupoxam, fluridone, pyrazolate, sulcotrione, carbamates such ascarbetamid, chlorbufam, chlorpropham, desmedipham, phenmedipham,vernolate, quinolinecarboxylic acids such as quinclorac, quinmerac,dichloropropionic acids such as dalapon, dihydrobenzofurans such asethofumesate, dihydrofuran-3-one such as flurtamone, dinitroanilinessuch as benefin, butralin, dinitramin, ethalfluralin, fluchloralin,isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin,trifluralin, dinitrophenols such as bromofenoxim, dinoseb,dinoseb-acetate, dinoterb, DNOC, minoterb-acetate, diphenyl ethers suchas acifluorfen-sodium, aclonifen, bifenox, chlornitrofen, difenoxuron,ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen,lactofen, nitrofen, nitrofluorfen, oxyfluorfen, dipyridyls such ascyperquat, difenzoquat-methylsulfate, diquat, paraquat-dichloride,imidazoles such as isocarbamid, imidazolinones such as imazamethapyr,imazapyr, imazaquin, imazethabenz-methyl, imazethapyr, oxadiazoles suchas methazole, oxadiargyl, oxadiazon, oxiranes such as tridiphane,phenols such as bromoxynil, ioxynil, phenoxyphenoxypropionic esters suchas clodinafop, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl,fenoxaprop-p-ethyl, fenthiapropethyl, fluazifop-butyl,fluazifop-p-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl,haloxyfop-p-methyl, isoxapyrifop, propaquizafop, quizalofop-ethyl,quizalofop-p-ethyl, quizalofop-tefuryl, phenylacetic acids such aschlorfenac, phenylpropionic acids such as chlorophenprop-methyl, ppiactive ingredients such as benzofenap, flumiclorac-pentyl, flumioxazin,flumipropyn, flupropacil, pyrazoxyfen, sulfentrazone, thidiazimin,pyrazoles such as nipyraclofen, pyridazines such as chloridazon, maleichydrazide, norflurazon, pyridate, pyridinecarboxylic acids such asclopyralid, dithiopyr, picloram, thiazopyr, pyrimidyl ethers such aspyrithiobac-acid, pyrithiobac-sodium, KIH-2023, KIH-6127, sulfonamidessuch as flumetsulam, metosulam, triazolecarboxamides such astriazofenamid, uracils such as bromacil, lenacil, terbacil, furthermorebenazolin, benfuresate, bensulide, benzofluor, butamifos, cafenstrole,chlorthal-dimethyl, cinmethylin, dichlobenil, endothall, fluorbentranil,mefluidide, perfluidone, piperophos.

Preferred herbicidal plant protectants are those of the sulfonylureatype such as amidosulfuron, azimsulfuron, bensulfuron-methyl,chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron,ethametsulfuron-methyl, flazasulfuron, halosulfuron-methyl,imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron,prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl,thifensulfuron-methyl, triasulfuron, tribenuron-methyl,triflusulfuron-methyl, tritosulfuron.

Preferred herbicidal plant protectants are furthermore those of thecyclohexenone type such as alloxydim, clethodim, cloproxydim,cycloxydim, sethoxydim and tralkoxydim.

Very especially preferred herbicidal active ingredients of thecyclohexenone type are: tepraloxydim (cf. AGROW, No. 243, 11.3.95, page21, caloxydim) and2-(1-[2-{4-chlorophenoxy}propyl-oxyimino]butyl)-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one,and of the sulfonylurea type:N-(((4-methoxy-6-[trifluoromethyl]-1,3,5-triazin-2-yl)amino)carbonyl)-2-(trifluoromethyl)benzenesulfonamide.

The fungicidal compositions comprise one or more of, for example, thefollowing fungicidal active ingredients: sulfur, dithiocarbamates andtheir derivatives, such as iron(III) dimethyldithiocarbamate, zincdimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganeseethylenebisdithiocarbamate, manganese zincethylenediaminebisdithiocarbamate, tetramethyl-thiuram disulfides,ammonia complex of zinc (N,N-ethylenebis-dithiocarbamate), ammoniacomplex of zinc (N,N′-propylene-bisdithiocarbamate), zinc(N,N′-propylenebisdithiocarbamate),N,N′-polypropylenebis(thiocarbamoyl)disulfide;

nitro derivatives, such as dinitro(1-methylheptyl)phenyl crotonate,2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl5-nitroisophthalate;heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate,2,4-dichloro-6-(o-chloroanilino)-s-triazine, 0,0-diethylphthalimidophosphonothioate,5-amino-1-[bis(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,2,3-dicyano-1,4-dithio-anthraquinone,2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl1-(butylcarbamoyl)-2-benzimidazolecarbamate,2-methoxycarbonyl-aminobenzimidazole, 2-(2-furyl)benzimidazole,2-(4-thiazolyl)-benzimidazole,N-(1,1,2,2-tetrachloroethylthio)tetrahydro-phthalimide,N-trichloromethylthiotetrahydrophthalimide,N-trichloromethylthiophthalimide,N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfodiamide,5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,2-thiocyanato-methylthiobenzothiazole,1,4-dichloro-2,5-dimethoxybenzene,4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine-2-thiol1-oxide, 8-hydroxyquinoline or its copper salt,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide,2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide,2,4,5-trimethylfuran-3-carboxanilide,N-cyclohexyl-2,5-dimethylfuran-3-carboxamide,N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,2-methylbenzanilide, 2-iodobenzanilide,N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide,1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,2,6-dimethyl-N-tridecylmorpholine or its salts,2,6-dimethyl-N-cyclododecylmorpholine or its salts,N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,N-[3-(p-tert-butyl-phenyl)-2-methylpropyl]piperidine,1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolylurea,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,(2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole,α-(2-chlorophenyl)-α-(4-chloro-phenyl)-5-pyrimidinemethanol,5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,bis(p-chlorophenyl)-3-pyridinemethanol,1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,1,2-bis(3-methoxy-carbonyl-2-thioureido)benzene,strobilurins such as methylE-methoxyimino-[α-(o-tolyloxy)-o-tolyl]acetate, methylE-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate,N-methyl-E-methoxyimino-[α-(2-phenoxyphenyl)]acetamide,N-methyl-E-methoxyimino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide,anilinopyrimidines such as N-(4,6-dimethylpyrimidin-2-yl)aniline,N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline,N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline,phenylpyrroles such as4-(2,2-difluoro-1,3-benzodioxol-4-yl)-pyrrole-3-carbonitrile,cinnamamides such as3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)-acryloylmorpholine,and a variety of fungicides such as dodecylguanidine acetate,3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide,hexachlorobenzene, methylN-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)-alanine methyl ester,N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone,DL-N-(2,6-dimethylphenyl)-N-(phenyl-acetyl)alanine methyl ester,5-methyl-5-vinyl-3-(3,5-dichloro-phenyl)-2,4-dioxo-1,3-oxazolidine,3-[3,5-dichlorophenyl-(5-methyl-5-methoxymethyl]-1,3-oxazolidine-2,4-dione,3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-di-carboximide,2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamide,1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole,2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol,N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoro-methyl-3-chloro-2-aminopyridine,1-((bis(4-fluorophenyl)methyl-silyl)methyl)-1H-1,2,4-triazole.

Useful growth regulators are, for example, the group of thegibberellins. These include, for example, the gibberellins GA₁, GA₃,GA₄, GA₅ and GA₇ and the like, and the correspondingexo-16,17-dihydrogibberellins and the derivatives thereof, for examplethe esters with C₁-C₄-carboxylic acids. Preferred in accordance with theinvention is exo-16,17-dihydro-GA₅-13-acetate.

In accordance with one embodiment of the present invention, the activeingredient component (a) consists essentially of one or more of thefollowing preferred active ingredients: bentazone, difenzoquat,pendimethalin, quinclorac, cycloxydim, quinmerac, sethoxydim,cinidon-ethyl, mecoprop, mecoprop-P, dichlorprop, chloridazon, dicamba,metobromuron, profoxydim, tritosulfuron, diflufenzopyr, s-dimethenamid,cyanazine, picolinafen, cyclosulfamuron, imazamethabenz-methyl,imazaquin, acifluorfen, nicosulfuron, sulfur, dithianon, tridemorph,metiram, nitrothal-isopropyl, thiophanate-methyl, metholachlor,triforine, cerbendazim, vinclozolin, dodine, fenpropimorph,epoxiconazole, kresoxim-methyl, pyraclostrobin, dimoxystrobin,cyazofamid, fenoxalin, dimethomorph, metconazole, dimethoate,chlorfenvinphos, phorate, fenbutatin oxide, chrorfenapyr, simazine,bensulforon, flufenoxuron, terflubenzuron, alpha-cypermetrin,cypermethrin, hydramethylnon, terbufos, temephos, halofenozide,flocoumafen, triazamate, flucythrinate, hexythiazox, dazomet,chlorocholin chloride, mepiquat-chloride, prohexadion-calcium, or of oneor more of the following very especially preferred active ingredients:metazachlor, paraquat, glyphosate, imazethaphyr, tepraloxydim, imazapic,imazamox, acetochlor, atrazine, tebufenpyrad, trifluralin, pyridaben.

In particular, the present invention relates to compositions comprisinghigh percentages of active ingredient (concentrates). Thus, as a rule,component (a) amounts to more than 10% by weight, preferably more than15% by weight and in particular more than 20% by weight of the totalweight of the composition. On the other hand, as a rule, component (a)expediently amounts to less than 80% by weight, preferably less than 70%by weight and in particular less than 60% by weight of the total weightof the composition.

Besides, the formulations according to the invention may compriseauxiliaries and/or additives which are conventionally used in thepreparation of formulations used for agrotechnical applications, inparticular in the field of crop protection. These include, for example,surfactants, dispersants, wetters, thickeners, organic solvents,cosolvents, antifoams, carboxylic acids, preservatives, stabilizers andthe like.

In accordance with a particular embodiment of the present invention, thecompositions comprise at least one (further) surfactant assurface-active component (c). In this context, the term “surfactant”refers to interface- or surface-active agents.

Component (c) is added in particular in the form of a dispersant oremulsifier, mainly for dispersing a solid in suspension concentrates.Moreover, parts of component (c) may act as wetters.

Surfactants which can be used in principle are anionic, cationic,amphoteric and nonionic surfactants, including polymer surfactants andsurfactants with heteroatoms in the hydrophobic group.

The anionic surfactants include, for example, carboxylates, inparticular alkali metal, alkaline earth metal and ammonium salts offatty acids, for example potassium stearate, which are usually alsoreferred to as soaps; acyl glutamates; sarcosinates, for example sodiumlauroyl sarcosinate; taurates; methylcelluloses; alkyl phosphates, inparticular alkyl esters of mono- and diphosphoric acid; sulfates, inparticular alkyl sulfates and alkyl ether sulfates; sulfonates,furthermore alkylsulfonates and alkylarylsulfonates, in particularalkali metal, alkaline earth metal and ammonium salts of arylsulfonicacids and of alkyl-substituted arylsulfonic acids, alkylbenzenesulfonicacids, such as, for example, lignosulfonic acid and phenolsulfonic acid,naphthalene- and dibutylnaphthalenesulfonic acids, ordodecylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl methyl estersulfonates, condensates of sulfonated naphthalene and derivativesthereof with formaldehyde, condensates of naphthalenesulfonic acids,phenol- and/or phenolsulfonic acids with formaldehyde or withformaldehyde and urea, mono- or dialkyl sulfosuccinates; and proteinhydrolyzates and lignin-sulfite waste liquors. The abovementionedsulfonic acids are advantageously used in the form of their neutral or,if appropriate, basic salts.

The cationic surfactants include, for example, quaternized ammoniumcompounds, in particular alkyltrimethylammonium halides,dialkyldimethylammonium halides, alkyltrimethylammonium alkyl sulfates,dialkyldimethylammonium alkyl sulfates and pyridine and imidazolinederivatives, in particular alkylpyridinium halides.

The nonionic surfactants include, for example, further alkoxylates,mainly ethoxylates, and nonionic surfactants, in particular

-   -   fatty alcohol polyoxyethylene esters, for example lauryl alcohol        polyoxyethylene ether acetate,    -   alkyl polyoxyethylene ethers and alkyl polyoxypropylene ethers,        for example of linear fatty alcohols, alkylaryl alcohol        polyoxyethylene ethers, for example octylphenol polyoxyethylene        ether,    -   alkoxylated animal and/or vegetable fats and/or oils, for        example corn oil ethoxylates, castor oil ethoxylates, tallow fat        ethoxylates,    -   glycerol esters such as, for example, glycerol monostearate,    -   fatty alcohol alkoxylates and oxo alcohol alkoxylates, in        particular of the linear type R₅O—(R₃O)_(r)(R₄O)_(s)R₂₀ where R₃        and R₄ independently of one another ═C₂H₄, C₃H₆, C₄H₈ and R₂₀═H,        or C₁-C₁₂-alkyl, R₅═C₃-C₃₀-alkyl or C₆-C₃₀-alkenyl, r and s        independently of one another are 0 to 50, where one of these        must be other than 0, and oleyl alcohol polyoxyethylene ether,    -   alkylphenol alkoxylates such as, for example, ethoxylated        isooctylphenol, octylphenol or nonylphenol, tributylphenyl        polyoxyethylene ethers,    -   fatty amine alkoxylates, fatty acid amide alkoxylates and fatty        acid diethanolamide alkoxylates, in particular their        ethoxylates,    -   sugar surfactants, sorbitol esters such as, for example,        sorbitan fatty acid esters (sorbitan monooleate, sorbitan        tristearate), polyoxyethylene sorbitan fatty acid esters,        alkylpolyglycosides, N-alkylgluconamides,    -   alkylmethyl sulfoxides,    -   alkyldimethylphosphine oxides such as, for example,        tetradecyldimethylphosphine oxide.

The amphoteric surfactants include, for example, sulfobetaines,carboxybetaines and alkyldimethylamine oxides, for exampletetradecyldimethylamine oxide.

The polymeric surfactants include, for example, di-, tri- andmulti-block polymers of the type (AB)_(x), ABA and BAB, for exampleoptionally end-capped ethylene oxide/propylene oxide block copolymers,for example ethylenediamine-EO/PO block copolymers, polystyrene blockpolyethylene oxide, and AB comb polymers, for example polymethacrylatecomb polyethylene oxide.

Further surfactants to be mentioned in the present context by way ofexample are perfluoro surfactants, silicone surfactants, for examplepolyether-modified siloxanes, phospholipids such as, for examplelecithin or chemically modified lecithins, amino acid surfactants, forexample N-lauroylglutamate, and surface-active homo- and copolymers, forexample polyvinylpyrrolidone, polyacrylic acids in the form of theirsalts, polyvinyl alcohol, polypropylene oxide, polyethylene oxide,maleic anhydride/isobutene copolymers and vinylpyrrolidone/vinyl acetatecopolymers.

Unless specified, the alkyl chains of the above-mentioned surfactantsare linear or branched radicals, usually having 8 to 20 carbon atoms.

The further surfactant as regards component (c) is preferably selectedfrom among nonionic surfactants. Preferred among the nonionicsurfactants are, in particular, those with HLB values ranging from 2 to16, preferably from 5 to 16, in particular from 8 to 16.

As a rule, component (c)—if present—amounts to less than 50% by weight,preferably less than 15% by weight and in particular less than 5% byweight of the total weight of the composition.

In accordance with a particular embodiment of the present invention, thecompositions comprise at least one further auxiliary as component (d).

Component (d) can fulfill a variety of purposes. Suitable auxiliariesare chosen in the customary manner by the skilled worker to suit therequirements.

For example, further auxiliaries are selected from among

-   (d1) solvents or diluents;-   (d2) emulsifiers, delayed-release agents, pH buffers, antifoams.

Besides water, the compositions may comprise further solvents of solublecomponents or diluents of insoluble components of the composition.

Examples which are useful in principle are mineral oils, synthetic oils,vegetable oils and animal oils, and low-molecular-weight hydrophilicsolvents such as alcohols, ethers, ketones and the like.

Those which must therefore be mentioned are, firstly, aprotic or apolarsolvents or diluents, such as mineral oil fractions of medium to highboiling point, for example kerosene and diesel oil, furthermore coal taroils, hydrocarbons, paraffin oils, for example C₈- to C₃₀-hydrocarbonsof the n- or isoalkane series or mixtures of these, optionallyhydrogenated or partially hydrogenated aromatics or alkylaromatics fromthe benzene or naphthalene series, for example aromatic orcycloaliphatic C₇- to C₁₈-hydrocarbon compounds, aliphatic or aromaticcarboxylic acid esters or dicarboxylic acid esters, or fats or oils ofvegetable or animal origin, such as mono-, di- and triglycerides, inpure form or in the form of a mixture, for example in the form of oilyextracts of natural materials, for example olive oil, soya oil,sunflower oil, castor oil, sesame seed oil, corn oil, groundnut oil,rapeseed oil, linseed oil, almond oil, castor oil, safflower oil, andtheir raffinates, for example hydrogenated or partially hydrogenatedproducts thereof and/or their esters, in particular the methyl and ethylesters.

Examples of C₈- to C₃₀-hydrocarbons of the n- or isoalkane series are n-and isooctane, -decane, -hexadecane, -octadecane, -eicosane, andpreferably hydrocarbon mixtures such as liquid paraffin (technical-gradeliquid paraffin may comprise up to approximately 5% aromatics) and aC₁₈-C₂₄ mixture which is commercially available from Texaco under thename Spraytex oil.

The aromatic or cycloaliphatic C₇ to C₁₈ hydrocarbon compounds include,in particular, aromatic or cycloaliphatic solvents from the series ofthe alkylaromatics. These compounds may be unhydrogenated, partiallyhydrogenated or fully hydrogenated. Such solvents include, inparticular, mono-, di- or trialkylbenzenes, mono-, di- ortrialkyl-substituted tetralins and/or mono-, di-, tri- ortetraalkyl-substituted naphthalenes (alkyl is preferably C₁-C₆-alkyl).Examples of such solvents are toluene, o-, m-, p-xylene, ethylbenzene,isopropylbenzene, tert-butylbenzene and mixtures, such as the Exxonproducts sold under the names Shelisol and Solvesso, for exampleSolvesso 100, 150 and 200.

Examples of suitable monocarboxylic esters are oleic esters, inparticular methyl oleate and ethyl oleate, lauric esters, in particular2-ethylhexyl laurate, octyl laurate and isopropyl laurate, isopropylmyristate, palmitic esters, in particular 2-ethylhexyl palmitate andisopropyl palmitate, stearic esters, in particular n-butyl stearate and2-ethylhexyl 2-ethylhexanoate.

Examples of suitable dicarboxylic esters are adipic esters, inparticular dimethyl adipate, di-n-butyl adipate, di-n-octyl adipate,di-iso-octyl adipate, also referred to as bis(2-ethylhexyl) adipate,di-n-nonyl adipate, diisononyl adipate and ditridecyl adipate; succinicesters, in particular di-n-octyl succinate and diisooctyl succinate, anddi(isononyl)cyclohexane 1,2-dicarboxylate.

As a rule, the above-described aprotic solvents or diluents amount toless than 80% by weight, preferably less than 50% by weight and inparticular less than 30% by weight of the total weight of thecomposition.

Some of these aprotic solvents or diluents may also have adjuvantproperties, that is to say in particular synergistic properties. Thisapplies in particular to said mono- and dicarboxylic esters. From thispoint of view, such adjuvants, perhaps in the form of a part of afurther formulation (stand-alone product), may also be mixed with thealcohol alkoxylates according to the invention or with compositionscomprising them at an expedient point in time, as a rule shortly priorto application.

Secondly, solvents or diluents which must be mentioned are protic orpolar solvents or diluents, for example C₂-C₈-monoalcohols such asethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol,cyclohexanol and 2-ethylhexanol, C₃-C₈-ketones such as diethyl ketone,t-butyl methyl ketone and cyclohexanone, and aprotic amines such asN-methyl- and N-octylpyrrolidone.

As a rule, the above-described protic or polar solvents or diluentsamount to less than 80% by weight, preferably less than 50% by weightand in particular less than 30% by weight of the total weight of thecomposition.

Sedimentation inhibitors may also be used, in particular for suspensionconcentrates. Their main purpose is rheological stabilization. Productswhich must be mentioned in this context are, in particular, mineralproducts, for example bentonites, talcites and herctorites.

Other additions which may be useful can be found for example amongmineral salt solutions which are employed for alleviating nutritionaland trace element deficiencies, nonphytotoxic oils and oil concentrates,antidrift reagents, antifoams, in particular the silicone type products,for example Silicon SL, which is sold by Wacker, and the like.

The formulations may be present in the form of an emulsifiableconcentrate (EC), a suspoemulsion (SE), an oil-in-water emulsion (O/W),a water-in-oil emulsion (W/O), an aqueous suspension concentrate, an oilsuspension concentrate (SC), a microemulsion (ME) and the like.

The compositions can be prepared in the manner known per se. To thisend, at least some of the components are combined. It must be taken intoconsideration that products, in particular commercially availableproducts, can be used whose constituents may contribute to differentcomponents. For example, a specific surfactant can be dissolved in anaprotic solvent, so that this product can contribute to differentcomponents. Furthermore, it is also possible in some circumstances forminor amounts of less desired substances to be introduced together withcommercially available products. As a rule, the products which have beencombined to a mixture must then be mixed thoroughly with each other togive a homogeneous mixture and, if appropriate, milled, for example inthe case of suspensions.

Mixing can be carried out in a manner known per se, for example byhomogenizing with suitable devices such as KPG stirrers or magneticstirrers.

Milling, too, is a process which is known per se. The milling elementsused can be made of glass or can be other mineral or metallic millingelements, as a rule in a size of from 0.1-30 mm and in particular 0.6-2mm. As a rule, the mixture is comminuted until the desired particle sizehas been achieved.

In general, milling may be carried out as a recirculation process, i.e.by continuously cycling an SC, or as a batch process, i.e. the completeand repeated processing of a batch.

Milling can be effected with conventional ball mills, bead mills oragitated mills, for example in a Dynomühle mill (Bachofen), with batchsizes of, for example, from 0.5 up to 1 liter in what is known as abatch operation. After several passes, in particular 4 to 6 passes (thesuspension being pumped through the mill with the aid of a peristalticpump), evaluation under the microscope reveals mean particle sizes offrom 0.5 to 10 μm.

As a rule, the compositions are diluted in the customary manner prior touse to obtain a form which is suitable for application. Dilution withwater or else aprotic solvents, for example by the tank mix method, ispreferred. The use in the form of a slurry preparation is preferred. Theapplication may be pre- or post-emergence. Post-emergence applicationresults in particular advantages.

The use according to the invention also encompasses the use of thealkoxylates according to the invention as “stand-alone” products. Tothis end, the alkoxylates are prepared in a suitable manner and addedshortly before use to the composition to be applied.

Particular advantages result mainly when carrying out a spray treatment.A customary spray mixture to be used as a tank mix involves diluting thecompositions according to the invention which already comprise at leastone alkoxylated branched alcohol—or further plant treatment productswith addition of at least one alkoxylated branched alcohol as“stand-alone” product—with water to apply, per hectare, approximately0.01 to 10, preferably approximately 0.05 to 5, in particular 0.1 to 1,kg of at least one alkoxylate according to the invention.

For the purposes of the present description, the terms alkyl encompassesstraight-chain or branched hydrocarbon groups such as methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl,n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, isodecyl,n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, isotridecyl,stearyl, n-eicosyl, preferably—unless otherwise specified—having 1 to 8,in particular 1 to 6 and especially preferably 1 to 4 carbon atoms inthe case of short-chain radicals and 5 to 30, in particular 12 to 24 andespecially preferably 8 to 20 carbon atoms in the case of long-chainradicals. The branched long-chain radicals include mainly 2-ethylhexyl,isononyl, isodecyl such as 2-propylheptyl, isoundecyl, isododecyl, andisotridecyl such as 2,4,8-tetramethyl-1-nonyl,3,4,6,8-tetramethyl-1-nonyl and 5-ethyl-4,7-dimethyl-1-nonyl.

For the purposes of the present description, quantities generally referto the total weight of a composition, unless otherwise specified. As arule, the term “essentially” refers in accordance with the invention toa percentage of at least 80%, preferably at least 90% and in particularat least 95%.

The invention is illustrated in greater detail by the examples whichfollow:

PREPARATION EXAMPLES Reference Examples 1 to 5 Preparation of theAlkoxylates (a) to (e) Reference Example 1 2-Propylheptanol+7 EO (a)

711 g of 2-propylheptanol (corresponding to 4.5 mol) together with 2.0 gof potassium hydroxide as alkoxylation catalyst were introduced into anautoclave. After a dehydration phase, 1386 g of ethylene oxide(corresponding to 31.5 mol) were passed in continuously at 150° C. Tocomplete the reaction, stirring was continued for 1 hour at the sametemperature. This gave 2080 g of the abovementioned product (a).

Reference Example 2 i-Tridecanol (Basis: Trimeric Butene)+6 EO+3 PO (b)

700 g of i-tridecanol (corresponding to 3.5 mol) together with 4.0 g ofpotassium hydroxide as alkoxylation catalyst were introduced into anautoclave. After a dehydration phase, 924 g of ethylene oxide(corresponding to 21.0 mol) were passed in continuously at 110 to 120°C. To complete the reaction, stirring was continued for 1 hour at thesame temperature. The temperature was then raised to 150° C., and 609 gof propylene oxide (corresponding to 10.5 mol) were added continuouslyto the reactor. When the pressure was constant, the temperature was heldfor two hours to complete the reaction. This gave 2210 g of theabovementioned product (b).

Reference Example 3 i-Decanol+10 EO+1.5 Pentene Oxide (c)

474 g of i-decanol (corresponding to 3.0 mol) together with 4.5 g ofpotassium hydroxide as alkoxylation catalyst were introduced into anautoclave. After a dehydration phase, 1320 g of ethylene oxide(corresponding to 30.0 mol) were passed in continuously at to 120° C. Tocomplete the reaction, stirring was continued for 1 hour at the sametemperature. The temperature was then raised to 160° C., and 387 g ofpentene oxide (corresponding to 4.5 mol) were added continuously to thereactor. When the pressure was constant, the temperature was held fortwo hours to complete the reaction. This gave 2180 g of theabovementioned product (c).

Reference Example 4 i-Decanol+3 EO (d)

1106 g of i-decanol (corresponding to 7.0 mol) together with 1.0 g ofpotassium hydroxide as alkoxylation catalyst were introduced into anautoclave. After a dehydration phase, 924 g of ethylene oxide(corresponding to 21.0 mol) were passed in continuously at 150° C. Tocomplete the reaction, stirring was continued for 1 hour at the sametemperature. This gave 2010 g of the abovementioned product (d).

Reference Example 5 i-Tridecanol (basis: trimeric butene)+3 EO (e)

1200 g of i-tridecanol (corresponding to 6.0 mol) together with 2.0 g ofpotassium hydroxide as alkoxylation catalyst were introduced into anautoclave. After a dehydration phase, 792 g of ethylene oxide(corresponding to 18.0 mol) were passed in continuously at 150° C. Tocomplete the reaction, stirring was continued for 1 hour at the sametemperature. This gave 1970 g of the abovementioned product (e).

Example 1 Herbicidal Efficacy of the Bentazone Formulations

The alkoxylates were applied by the tank mix method together withBasagran (480 g/l bentazone) or BAS 635 H (71.4% by weight oftritosulfuron). The application rate per ha was 0.250 kg of bentazone or8 g/ha tritosulfuron and 0.125 kg of a.s./ha alkoxylate according to theinvention or 0.250 kg/ha comparative adjuvant Atplus 411F (mineraloil/surfactant mixture; Uniqema). The herbicidal effect was assessed ina greenhouse experiment. The test plant used was white goosefoot(Chenepodium album; CHEAL) and the common morningglory (Pharbitis album;PHAAL).

The plants were sown directly or pricked out at a rate of 3-15 plantsper pot. When the active ingredient was applied, the plants were 5-16 cmin height. The test containers used were plastic pots containing loamysand and approximately 3% humus as substrate. The surfactants wereapplied by the tank mix method by spray application post-emergence in anautomated spray cabinet with a water application rate of 400 liters perhectare. The experimental period was 6 days to 4 weeks. Evaluation wascarried out using a scale of from 0% to 100%. 0% means no damage, 100%means complete damage.

The results of the assessment are compiled in tables 1 and 2 whichfollow.

TABLE 1 Bentazone Adjuvant Adjuvant (kg/ha) (kg/ha) CHEAL — 0.250 — 23%a 0.250 0.125 92% b 0.250 0.125 93% c 0.250 0.125 92% d 0.250 0.125 92%e 0.250 0.125 96% Comparison 0.250 0.250 50%

TABLE 2 Trito- sulfuron Adjuvant Adjuvant (kg/ha) (kg/ha) CHEAL PHAAL —0.250 — 35% 48% a 0.250 0.125 90% 65% b 0.250 0.125 92% 65% c 0.2500.125 90% 68% d 0.250 0.125 92% 65% e 0.250 0.125 90% 73% Comparison0.250 0.250 90% 62%It can be seen clearly that formulations with alkoxylate according tothe invention are considerably more effective than the comparativeformulation without adjuvant, or than the comparative formulation whichjust contain Atplus 411 F instead of alkoxylates according to theinvention.

1.-29. (canceled)
 30. A method of treating plants which comprisesapplying to the plants an active agent for the treatment of plants andas adjuvant an alkoxylated C₁₃-oxo alcohol or C₁₀-oxo alcohol selectedamong alcohol alkoxylates of the formula (I)R—O—(C_(m)H_(2m)O)_(x)—(C_(n)H_(2n)O)_(y)(C_(p)H_(2p)O)_(z)—H  (I) inwhich R is isotridecyl or isodecyl; x+y+z have a value of 1 to 100, andm=2, n=3, x>0, y>0, and z=0; or m=3, n=2, x>0, y>0, and z=0; or m=2,n=5, x>0, y>0, and z=0; or m=5, n=2, x>0, y>0, and z=0.
 31. The methodaccording to claim 30, wherein m=2, n=3, x has a value from 4 to 10, yhas a value from 2 to 5, the ratio of x to y is 1.5:1 to 3:1, and thetotal of x and y has a value from 6 to
 15. 32. The method according toclaim 30, wherein m=3, n=2, x has a value from 1 to 4, y has a valuefrom 4 to 10, the ratio of x to y is 1.5:1 to 1:6, and the total of xand y has a value from 5 to
 14. 33. The method according to claim 30,wherein m=2, n=5, wherein x has a value from 6 to 15, y has a value from0.5 to 2, the ratio of x to y is 4:1 to 5:1, and the total of x and yhas a value from 6.5 to
 17. 34. The method according to claim 30,wherein m=5, n=2, wherein x has a value from 0.5 to 2, y has a valuefrom 5 to 15, the ratio of x to y is 1:25 to 1:5, and the total of x andy has a value from 5.5 to
 17. 35. The method according to claim 30,wherein the alcohol is a C₁₃-oxo alcohol has a degree of branching inthe range from 1 to
 4. 36. The method according to claim 35, wherein theC₁₃-oxo alcohol is obtained by hydrogenation of hydroformylated trimericbutene or by hydrogenation of hydroformylated dimeric hexene.
 37. Themethod according to claim 36, wherein the C₁₃-oxo alcohol has a degreeof branching in the range from 2.1 to 2.5.
 38. The method according toclaim 30, wherein the alcohol is a C₁₀-oxo alcohol having a degree ofbranching in the range from 1 to
 4. 39. The method according to claim38, wherein the C₁₀-oxo alcohol is obtained by hydrogenation ofhydroformylated trimeric propene.
 40. The method according to claim 30,wherein the efficacy of said active agent for the treatment of plants isimproved.
 41. The method of claim 40, wherein the efficacy of the activeagent is improved through better uptake of the active agent by theplant.
 42. The method of claim 41, wherein the uptake of the activeagent takes place via the leaves of the plant.
 43. The method accordingto claim 30, wherein the alkoxylated alcohol is applied post-emergence.44. The method according to claim 30, wherein the alkoxylated alcohol isapplied by spraying on the plants.
 45. The method according to claim 30,wherein the alkoxylated alcohol is applied as a tank additive.